Perfluoropolyether group-containing silane compound, preparation method thereof, surface treatment agent and article

ABSTRACT

The present invention relates to a perfluoropolyether group-containing silane compound represented by formula (1): Rf—X 1 —X 2 —NQ k T 2-k , (1), and a method for preparing the same. The present invention also relates to a perfluoropolyether group-containing silane compound represented by formula (2), 
     
       
         
         
             
             
         
       
     
     and a method for preparing the same. The present invention also relates to a perfluoropolyether group-containing silane compound represented by formula (3), 
     
       
         
         
             
             
         
       
     
     and a method for preparing the same. The perfluoropolyether group-containing silane compound of the present invention can be used for a surface treatment agent so that the substrates such as glass etc processed by the surface treatment agent are excellent in anti-fouling, anti-fingerprint, scrape resistant and abrasion resistant performances. Moreover, the preparation method of each of the compounds of the present invention is simple in process, easy to operate and implement.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a bypass continuation application of InternationalApplication No. PCT/CN2018/087473, filed May 18, 2018, which claimspriority to Chinese Application No. 201810468845.1, filed May 16, 2018,which applications are incorporated herein by reference in theirentirety.

FIELD OF INVENTION

The present invention relates to a surface treatment agent, particularlyto a perfluoropolyether group-containing silane compound and preparationmethod thereof, a surface treatment agent comprising theperfluoropolyether group-containing silane compound as well as anarticle treated using the surface treatment agent.

BACKGROUND OF THE INVENTION

It is known in the prior art that when a substrate is treated by aperfluoropolyether group-containing silane compound, a membrane layer,which has the properties of hydrophobicity, oleophobicity, anti-fouling,low coefficient of friction and durability, can be formed on the surfacethereof. This is because that (1) perfluoropolyether in a molecule hasthe property of low surface energy, and (2) the siloxane group in amolecule can be bonded by dehydration condensation reaction to form achemical bond on the surface of a substrate. A surface treatment agentcontaining the composition can be uniformly dispersed onto a substratein the manner of spraying or vapor deposition, which forms a membranelayer having protection function via thermal curing. Since the membranelayer is only several nanometers thick and transparent, it will notinfluence the appearance and transparency of a substrate.

The membrane layer prepared with the existing perfluoropolyethergroup-containing silane compound has higher abrasion resistance, whichcan withstand reciprocating wear by steel wool over 5000 times, even upto ten thousands of times. The surface dynamic friction coefficient ofthe membrane layer can be reduced to 0.05 or so. However, there are manyproblems for the existing perfluoropolyether group-containing silanecompound, such as big difficulty in synthesis process, many preparationsteps, long preparation process, and raw materials with particularstructure not easy to be obtained, thereby resulting in high price andhigh production cost.

SUMMARY

For the technical problem in the prior art, the present inventionprovides a new perfluoropolyether group-containing silane compound and amethod for preparing the same.

In one aspect, the present invention provides a perfluoropolyethergroup-containing silane compound represented by formula (1):

Rf—X¹—X²—NQ_(k)T_(2-k)  (1);

In the formula, Rf isF—(CF₂)_(m)—(OC₄F₈)_(p)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—,here, p, q, r and s are separately independent and are integers of 0 ormore and 200 or less, the sum of p, q, r and s is at least 1, theexisting sequence and number of each repeating unit with p, q, r and sand bracketed with a brackets are arbitrary in the formula; in and t areseparately integers of 0 or more and 30 or less, Z is F or CF₃;

wherein, said separately independent refers to that said letters presentat each time in the chemical formula can be the same or differentnumerical values in the range thereof. For example, “p, q, r and s areseparately independent and are integers of 0 or more and 20 or less”refers to that p, q, r and s present at each time in the chemicalformula can represent as any same or different integers of 0 or more and200 or less. It can be understood that the definition of separatelyindependent hereinafter is the same as this.

X¹ is a bivalent organic group;

X² is carbonyl, sulfuryl or anhydride;

T, when present at each time, is separately independent and is hydroxyl,a hydrolysable group or hydrocarbon group;

Q, when present at each time, is separately independent and is —Y—SiR¹_(j)R² _(3-j); Y, when present at each time, is separately independentand is a bivalent organic group;

R¹, when present at each time, is separately independent and is alkoxy,hydroxyl or a group that can be hydrolyzed to hydroxyl group, wherein,preferably, R¹ is —OR³, in the formula, R³ is substituted orunsubstituted C₁₋₃alkyl, preferably, R³ is methyl, ethyl, propyl,isopropyl;

R², when present at each time, is separately independent and is C₁₋₂₂alkyl, or Q′, Q′ and Q has the same meaning, that is, Q′, when presentat each time, is also separately independently —Y—SiR¹ _(j)R² _(3-j); itcan be understood that Q′ hereinafter has the same meaning as that of Q,and both are similar.

j is separately independent in each of Q and Q′, that is, j in Q′ and jin Q may be the same or different number value, being an integerselected from 0˜3, the sum of j is 1 or more;

k is separately independently 1 or 2, preferably, k is 2.

In the above formula (1), Rf may also be the following formula (a) or(b):

CF₃—(OC₂F₄)_(r)—(OCF₂)_(s)—OCF₂—  (a):

In the formula, the sum of r and s is an integer of 10 or more and 200or less;

F—(CF₂)_(m)—(OC₄F₈)_(p)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—  (b):

In the formula, in and t are separately independent, in is an integer of1-16, t is an integer of 0-2, r and s are separately independent and areintegers of 1 or more and 200 or less, the sum of p, q, r and s is 10 ormore and 200 or less, the existing sequence and number of each repeatingunit with p, q, r and s and bracketed with brackets are arbitrary in theformula.

In the above formula (1), X¹ may be a group as shown below:

—R⁴—X³—X⁴—;

wherein, R⁴ is C₁₋₆ alkyl or substituted C₁₋₆ alkyl; X³ is a groupselected from —O—, —S—, ortho, meta- or para-phenylene, ortho-, meta- orpara-benzylidene, —C(O)O—, —CONR⁵—, —O—CONR⁵—, —Si(R⁶)₂—,—(Si(R⁶)₂O)_(f)—Si(R⁶)₂— and —(CH₂)_(g)—; R⁵, when present at each time,is separately independent and is a hydrogen atom, phenyl or C₁₋₆ alkyl;R⁶ is C₁₋₆ alkyl or substituted C₁₋₆ alkyl; X⁴ is a bivalent group; f,when present at each time, is separately independent and is an integerof 1˜100, g, when present at each time, is separately independent and isan integer of 1˜20;

Preferably, X⁴ is a group represented by —(R⁷)_(a)—(X⁵)_(b)—R⁸—,wherein:

R⁷ is —(CH₂)_(c)—, ortho-, meta-, or para-phenylene, or ortho-, meta-,or para-benzylidene; c is an integer of 1˜20;

a is 0 or 1; b is 0 or 1;

R⁸ is —(CH₂)_(d)—, ortho-, meta- or para-phenylene, or ortho-, meta-, orpara-benzylidene; d is an integer of 1˜20;

X⁵ is —(X⁶)_(e)—, X⁶, when present at each time, is separatelyindependent, and is a group selected from —O—, —S—, ortho-, meta- orpara-phenylene, ortho-, meta- or para-benzylidene, —C(O)O—, —CONR⁵—,—O—CONR⁵—, —Si(R⁶)₂—, —(Si(R⁶)₂O)_(f)—Si(R⁶)₂— and —(CH₂)_(g); R⁵, whenpresent at each time, is separately independent, and is a hydrogen atom,phenyl or C₁₋₆ alkyl; R⁶, when present at each time, is separatelyindependent, and is phenyl or C₁₋₆ alkyl; f, when present at each time,is separately independent, and is an integer of 1˜100; g, when presentat each time, is separately independent, and is an integer of 1˜20; e isan integer of 1˜10.

In the above formula (1), T, when present at each time, is separatelyindependent, and is selected from hydroxyl, —O(R⁷), C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₂₋₁₂ alkynyl and phenyl, R⁷ is C₁₋₁₂ alkyl, preferably, T,when present at each time, is separately independent, and is hydroxyl,or —O(R⁷), R⁷ is C₁₋₁₂ alkyl.

In another aspect, the present invention provides a perfluoropolyethergroup-containing silane compound having the following chemical generalformula (2),

Wherein, Rf is

-   -   q, r and s are separately independent and are integers of 0 or        more and 200 or less, the sum of q, r and s is at least 1, the        existing sequence of each repeating unit noted with q, r or s        and bracketed with brackets is arbitrary in the formula; in is        an integer of 1-16, t is 0 or 1, Z is a fluoride atom or        trifluoromethyl;    -   X is a bivalent organic group;    -   T, when present at each time, is separately independent and is        hydroxyl, a hydrolysable group or hydrocarbon group;    -   Q, when present at each time, is separately independent and is        —Y—SiR¹ _(j)R² _(3-j);    -   Y, when present at each time, is separately independent and is a        bivalent organic group;    -   R¹, when present at each time, is separately independent and is        alkoxy, hydroxyl or a group that can be hydrolyzed to a hydroxyl        group, wherein, preferably, it is alkoxy, and more preferably,        C₁₋₃ alkoxy;    -   R², when present at each time, is separately independent and is        C₁₋₂₂ alkyl or    -   Q′, Q′ and Q have the same meaning;    -   j is separately independent in each of Q and Q′, and is an        integer selected from    -   0 to 3, the sum of j is at least 1;    -   k is separately independent, and is 1 or 2, preferably k is 2.

In the above formula (2), preferably, X is a group represented by—(R³)_(a)—(X¹)_(b)—R⁴—, wherein:

R³ is —(CH₂)_(c)—, ortho-, meta- or para-phenylene, or ortho-, meta- orpara-benzylidene; c is an integer of 1˜20; a is 0 or 1;

R⁴ is —(CH₂)_(d)—, ortho-, meta- or para-phenylene, or ortho-, meta- orpara-benzylidene; d is an integer of 1˜20;

X¹ is —(X²)_(e)—;

b is 0 or 1;

X², when present at each time, is separately independent, and is a groupselected from —O—, —S—, ortho-, meta- or para-phenylene, ortho-, meta-or para-benzylidene, —C(O)O—, —CONR⁵—, —O—CONR⁵—, —Si(R⁶)₂—,—(Si(R⁶)₂O)_(f)—Si(R⁶)₂— and —(CH₂)_(g)—; R⁵, when present at each time,is separately independent, and is a hydrogen atom, phenyl or C₁₋₆ alkyl;R⁶, when present at each time, is separately independent, and is phenylor C₁₋₆alkyl; f, when present at each time, is separately independent,and is an integer of 1˜100; g, when present at each time, is separatelyindependent, and is an integer of 1˜20; e is an integer of 1˜10.

In the above formula (2), preferably X is C₁₋₂₀ alkylidene, —R³—X³—R⁴—or —X⁴—R⁴—, wherein, X³ is —O—, —S—, —C(O)O—, —CONR⁵—, —O—CONR⁵—,—Si(R⁶)₂—, —(Si(R⁶)₂O)_(f)—Si(R⁶)₂—,—O—(CH₂)_(h)—(Si(R⁶)₂O)_(r)—Si(R⁶)₂—,—CONR⁵—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—, —CONR⁵—(CH₂)_(h)—N(R⁵)— or—CONR⁵-(ortho-, meta- or para-phenylene)-Si(R⁶)₂—; X⁴ is —S—, —C(O)O—,—CONR⁵—, —O—CONR⁵—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—,—CONR⁵—(CH₂)_(h)—N(R⁵)— or —CONR⁵-(ortho-, meta- orpara-phenylene)-Si(R⁶)₂—; R³ is —(CH₂)_(c)—, ortho-, meta- orpara-phenylene, or ortho-, meta- or para-benzylidene; R⁴ is —(CH₂)_(d)—,ortho-, meta- or para-phenylene, or ortho-, meta- or para-benzylidene;R⁵, when present at each time, is separately independent, and is ahydrogen atom, phenyl or C₁₋₆ alkyl, R⁶, when present at each time, isseparately independent, and is phenyl or C₁₋₆ alkyl; h is an integer of1˜20; f, when present at each time, is separately independent, and is aninteger of 1˜100.

More preferably, R³ is —(CH₂)_(c)—, R⁴ is —(CH₂)_(d)—, wherein, c is aninteger of 1˜20; d is an integer of 1˜20.

Further preferably, X is C₁₋₂₀ alkylidene, —(CH₂)_(c)—O—(CH₂)_(d),—(CH₂)_(c)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—(CH₂)_(d)—,—(CH₂)_(c)—O—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—(CH₂)_(d)—, c is aninteger of 1˜20; d is an integer of 1˜20; R⁶, when present at each time,is separately independent, and is phenyl or C₁₋₆ alkyl; h is an integerof 1˜20; f, when present at each time, is separately independent, and isan integer of 1˜100.

Further preferably, X is selected from the following groups: —CH₂—,—(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₆—, —CH₂C₆H₄—, —CH₂OCH₂—,—CH₂O(CH₂)₂—, —CH₂O(CH₂)₃—, —CH₂O(CH₂)₆—, —CH₂C₆H₄—OCH₂—, —CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—, —CON(Ph)-(CH₂)₃—, Ph is phenyl, —CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆—, Ph is phenyl, —CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—, —CH₂O—CONH—(CH₂)₃—, —CH₂O—CONH—(CH₂)₆—,—C(O)O—(CH₂)₃—, —C(O)O—(CH₂)₆—, —S—(CH₂)₃—, —(CH₂)₂S(CH₂)₃—,—CH₂O—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—.

Preferably, T, when present at each time, is separately independent, andis selected from hydroxyl, —O(R⁷), C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂alkynyl and phenyl, R⁷ is C₁₋₁₂ alkyl.

Further preferably, T, when present at each time, is separatelyindependent, and is hydroxyl, or —O(R⁷), R⁷ is C₁₋₁₂ alkyl.

Preferably, in Q of formula (2), j is 3.

Preferably, the perfluoropolyether group-containing silane compound asrepresented by the formula (2) has the number average molecule weight of500-10,000, preferably 1000-8000, more preferably 3000-6000.

Still in another aspect, the present invention provides aperfluoropolyether group-containing silane compound having the followingchemical general formula (3),

-   -   Wherein, Rf is        F—(CF₂)_(m)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—,        q, r, and s are separately independent and are integers of 0 or        more and 200 or less, the sum of q, r and s is at least 1, the        existing sequence of each repeating unit noted with q, r or s        and bracketed with brackets is arbitrary in the formula; in is        an integer of 1-16, t is 0 or 1, Z is a fluoride atom or        trifluoromethyl;    -   X is a bivalent organic group, preferably X is C₁₋₆ alkylidene,        —CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent on phenyl ring;    -   Y¹, Y² are separately independently C₁₋₆ alkylidene;    -   Q¹, Q² are separately independently alkoxy, hydroxyl or a group        that can be hydrolyzed to hydroxyl group;    -   R¹, R² are separately independently C₁₋₆ alkyl or phenyl;    -   n is an integer of 1-3, preferably, n is 3.

Preferably, in the formula (3), Rf is CF₃(OC₂F₄)_(r)(OCF₂)_(s)OCF₂,wherein, r, s are separately independent and are integers of 0 or moreand 200 or less, the sum of r, s is at least 1, the existing sequence ofeach repeating unit noted with r, s and bracketed with brackets isarbitrary in the formula;

-   -   X is C₁₋₆ alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which has a        substitutent on phenyl ring;    -   Y¹, Y² are separately independently C₁₋₆ alkylidene;    -   Q¹, Q² are separately independently alkoxy, hydroxyl or a group        that can be hydrolyzed to hydroxyl group;    -   R¹, R² are separately independently C₁₋₆alkyl or phenyl.

Preferably, in the formula (3), X is —CH₂—, —CH(CH₃)—, —C₂H₄—, —C₃H₆—.

Preferably, in the formula (3), Y¹ and Y² are separately —(CH₂)₃—.

Preferably, in the formula (3), Q¹, Q² are separately independently C₁₋₆alkoxy, more preferably, Q¹, Q² are separately independently —OCH₃,—OCH(CH₃)₂, —OC₂H₅ or —OC₃H₇.

Preferably, the perfluoropolyether group-containing silane compound asrepresented by the formula (3) has the number average molecule weight of500-10,000, preferably 1000-8000, more preferably 3000-6000.

In one aspect, the present invention also provides a method forpreparing a perfluoropolyether group-containing silane compoundrepresented by the formula (1),

Rf—X¹—X²—NQ_(k)T_(2-k)  (1);

which comprises:

Rf—X¹—X²—OH+acyl halogenation agent+aminosilane couplingagent→Rf—X¹—X²—NQ_(k)T_(2-k)

In the formula, Rf isF—(CF₂)_(m)—(OC₄F₈)_(p)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC (Z)F—(CF₂)_(t)—, here, p, q, r and s are separately independent and areintegers of 0 or more and 200 or less, the sum of p, q, r and s is atleast 1, the existing sequence and number of each repeating unit with p,q, r and s and bracketed with brackets are arbitrary in the formula; inand t are separately integers of 0 or more and 30 or less, Z is F orCF₃;

X¹ is a bivalent organic group;

X² is carbonyl, sulfuryl or anhydride;

T, when present at each time, is separately independent and is hydroxyl,hydrolysable group or hydrocarbon group;

Q, when present at each time, is separately independent and is —Y—SiR¹_(j)R² _(3-j),

Y, when present at each time, is separately independent and is abivalent organic group;

R¹, when present at each time, is separately independent and is alkoxy,hydroxyl or a group that can be hydrolyzed to hydroxyl group;

R², when present at each time, is separately independent and is C₁₋₂₂alkyl or Q′, wherein Q′ and Q has the same meaning;

j is separately independent in each of Q and Q′, being an integerselected from 0 to 3, the sum of j is 1 or more;

k is separately independent and is 1 or 2.

Preferably, acyl halogenation agent is (COCl)₂, SOCl₂, POCl₃, PCl₅ orSOBr₂.

Preferably, aminosilane coupling agent is HNQ_(k)T_(2-k), the meaning ofQ, T, k is the same as that defined in the above formula (1).

In another aspect, the present invention also provides a method forpreparing a perfluoropolyether group-containing silane compoundrepresented by the formula (2),

said method comprises:

reacting and converting a compound of formula Rf—CH₂—O—X—COOH with acylhalogenation agent and aminosilane coupling agent to obtain aperfluoropolyether group-containing silane compound of formula (2),

wherein, Rf is:

q, r and s are separately independent and are integers of 0 or more and200 or less, the sum of p, q, r and s is at least 1, the existingsequence of each repeating unit noted with q, r or s and bracketed withbrackets is arbitrary in the formula; in is an integer of 1-16, t is 0or 1, Z is a fluoride atom or trifluoromethyl;

X is a bivalent organic group;

T, when present at each time, is separately independent and is hydroxyl,hydrolysable group or hydrocarbon group;

Q, when present at each time, is separately independent and is —Y—SiR¹_(j)R² _(3-k); Y, when present at each time, is separately independentand is a bivalent organic group; R¹, when present at each time, isseparately independent and is alkoxy, hydroxyl or a group that can behydrolyzed to hydroxyl group; R², when present at each time, isseparately independent and is C₁₋₂₂ alkyl or Q′, wherein Q′ and Q havethe same meaning; j is separately independent in each of Q and Q′, andis an integer selected from 0˜3, the sum of j is 1 or more;

k is separately independent, and is 1 or 2.

Preferably, the acyl halogenation agent is acyl halide, preferably acylchloride, and more preferably oxalyl chloride.

Preferably, the aminosilane coupling agent is HNQ_(k)T_(2-k), wherein Qis —Y—SiR¹ _(j)R² _(3-j); Y is a bivalent organic group; R′ is alkoxy,hydroxyl or a group that can be hydrolyzed to hydroxyl group; R² isC₁₋₂₂ alkyl or Q′, wherein Q′ and Q have the same meaning; j isseparately independent in each of Q and Q′, and is an integer selectedfrom 0˜3, the sum of j is a 1 or more; k is separately independent, andis 1 or 2.

Preferably, preparation of the starting raw material Rf—CH₂—O—X—COOHused in the forementioned reaction comprises:

Step 1: first reacting the compound of formula Rf—CH₂OH with a base inthe presence of a solvent, and then making a nucleophilic substitutionreaction with a compound of formula L-X-G, obtaining a compound offormula Rf—CH₂—O—X-G, wherein in the formula L-X-G, L is a leaving groupor atom where a nucleophilic substitution reaction can occur, X is abivalent organic group, G is a group that can be hydrolyzed tocarboxylic acid,

Step 2: chemically converting the compound of formula Rf—CH₂—O—X-G toobtain a compound of formula Rf—CH₂—O—X—COOH,

Preferably, the base in step 1 is selected from inorganic base ororganic base; inorganic base is preferably selected from at least one ofLiOH, NaOH, KOH, K₂CO₃, Na₂CO₃, Cs₂CO₃, NaH, t-BuOK; organic base ispreferably selected from at least one of DIPEA(N,N-diisopropylethylamine), DBU (1,8-diazabicycloundec-7-ene),1,1,3,3-tetramethylguanidine.

Preferably, in the compound of formula L-X-G of step 1, L is selectedfrom: chlorine atom, bromine atom, iodine atom, or other leavinggroup(s) that can undergo nucleophilic substitution reaction; G isselected from: at least one group of ester group, nitrile group, amidegroup, or substituted amide group.

Preferably, the base in step 2 is selected from at least one of sodiumhydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide.

Preferably, the acid in step 2 is selected from: hydrochloric acid,sulfuric acid, phosphoric acid or nitric acid.

Still in another aspect, the present invention also provides a methodfor preparing a perfluoropolyether group-containing silane compoundrepresented by the formula (3),

The method comprises: reacting Rf—CH₂—O—X—COOH with acyl halogenationagent and aminosilane coupling agent

wherein, Rf isF—(CF₂)_(m)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—, q, r,and s are separately independent and are integers of 0 or more and 200or less, the sum of q, r and s is at least 1, the existing sequence ofeach repeating unit noted with q, r or s and bracketed with brackets isarbitrary in the formula; in is an integer of 1-16, t is 0 or 1, Z is afluoride atom or trifluoromethyl;

X is a bivalent organic group, preferably X is C₁₋₆ alkylidene,—CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent on phenyl ring;

Y¹, Y² are separately independently C₁₋₆ alkylidene;

Q¹, Q² are separately independently alkoxy, hydroxyl or a group that canbe hydrolyzed to hydroxyl group;

R¹, R² are separately independently C₁₋₆ alkyl or phenyl;

n is an integer of 1-3, preferably, n is 3.

Preferably, the acyl halogenation agent is (COCl)₂, SOCl₂, POCl₃, PCl₅or SOBr₂.

Preferably, preparation of the starting raw material Rf—CH₂—O—X—COOHused in the forementioned reaction comprises:

Step 1: first reacting the compound of formula Rf—CH₂OH with a base inthe presence of a solvent, and then making a nucleophilic substitutionreaction with a compound of formula L-X-G, wherein, L is a leaving groupor atom where a nucleophilic substitution reaction can occur, G is agroup that can be hydrolyzed to carboxylic acid; X is a bivalent organicgroup, preferably X is C₁₋₆ alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which hasa substitutent on phenyl ring; obtaining an esteryl perfluorinatedpolyether compound of formula Rf—CH₂—O—X-G,

Step 2: hydrolyzing the compound of formula Rf—CH₂—O—X-G to obtain acarboxyl perfluorinated polyether compound of formula Rf—CH₂—O—X—COOH,

Wherein, Rf and X have the same meaning as those defined in theforementioned formula (3).

The base in step 1 is selected from inorganic base or organic base;inorganic base is preferably selected from at least one of LiOH, NaOH,KOH, K₂CO₃, Na₂CO₃, Cs₂CO₃, NaH, t-BuOK; organic base is preferablyselected from at least one of DIPEA, DBU, 1,1,3,3-tetramethylguanidine.

Preferably, in the compound of formula L-X-G, L is chlorine atom,bromine atom, or iodine atom; G is ester group, nitrile group, amidegroup, or substituted amide group.

The solvent is fluorinated solvent, preferably hydrofluoroether orfluorinated hydrocarbon.

Preferably, the base in step 2 is selected from at least one of sodiumhydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide.

Preferably, the acid in step 2 is selected from inorganic acid, and morepreferably selected from at least one of hydrochloric acid, sulfuricacid, phosphoric acid or nitric acid.

Preferably, the aminosilane coupling agent is bis(alkoxy silane alkyl)amine.

Preferably, in the formula (3), Rf is CF₃(OC₂F₄)_(r)(OCF₂)_(s)OCF₂,wherein, r, s are separately independent and are integers of 0 or moreand 200 or less, the sum of r, s is at least 1, the existing sequence ofeach repeating unit noted with r, s and bracketed with brackets isarbitrary in the formula; preferably, the sum of r, s is 20-100, morepreferably, the sum of r, s 30-60;

X is C₁₋₆ alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent onphenyl ring;

Y¹, Y² are separately independently C₁₋₆ alkylidene;

Q¹, Q² are separately independently alkoxy, hydroxyl or a group that canbe hydrolyzed to hydroxyl group;

R¹, R² are separately independently C₁₋₆alkyl or phenyl.

The present invention also provides a surface treatment agent, whichcomprises the above perfluoropolyether group-containing silane compoundas represented by formula (1), formula (2) or formula (3), the surfacetreatment agent further comprises a fluorinated solvent, the fluorinatedsolvent is hydrofluoroether.

Preferably, the surface treatment agent comprises 0.01-30 wt %,preferably 0.05-20 wt % or 10-20 wt % of the above perfluoropolyethergroup-containing silane compound.

The present invention also relates to an article having a coating formedby the above surface treatment agent, and the coating has a surfacewater contact angle of at least 110 degrees and a dynamic frictioncoefficient of not more than 0.05.

The article may be but not limited to display screen of opticalcomponent, smartphone, Tablet or computer.

The perfluoropolyether group-containing silane compound of the presentinvention has good hydrophobicity, lipophobicity, smoothness, steelvelvet abrasion resistance and eraser abrasion resistance. In addition,the preparation process of the perfluoropolyether group-containingsilane compound of the present invention reduces the difficulty ofsynthesis, simples the step process, and greatly reduces the productioncost. This is mainly demonstrated in that: the used materials are allcommercially available conventional products and are easy to beobtained; the reactions that perfluoropolyether was modified to give anew intermediate, and the reactions that the new intermediate iscombined with silane coupling agent are all the conventional chemicalreactions, the conditions of which are mild and easy to control; thereare fewer steps required for product synthesis, simpler steps forseparation and purification, and more advantageous production costs.

The surface treatment agent prepared by the perfluoropolyether compoundof the present invention can be used for the surface of a substrate suchas a glass, such that the substrate such as the glass treated by thesurface treatment agent are excellent in anti-fouling, anti-fingerprint,scrape resistant and abrasion resistant performances.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is NMR spectrum of esteryl perfluoropolyether compounds (M1) inSynthesis Example 1.

FIG. 2 is NMR spectrum of carboxyl perfluoropolyether compounds (M2) inSynthesis Example 1.

FIG. 3 is NMR spectrum of perfluoropolyether silane compounds (A1) inSynthesis Example 1.

FIG. 4 is NMR spectrum of esteryl perfluoropolyether compounds (M3) inSynthesis Example 2.

FIG. 5 is NMR spectrum of carboxyl perfluoropolyether compounds (M4) inSynthesis Example 2.

FIG. 6 is NMR spectrum of perfluoropolyether silane compounds (A2) inSynthesis Example 2.

FIG. 7 is NMR spectrum of esteryl perfluoropolyether compounds (M6) inSynthesis Example 3.

FIG. 8 is NMR spectrum of perfluoropolyether compounds (A3) in SynthesisExample 3.

FIG. 9 is infrared spectrum of carboxyl perfluoropolyether compounds(M2) in Synthesis Example 3.

DETAILED DESCRIPTION OF THE INVENTION

In sequence to make the purpose, technical solution and advantage of thepresent invention clearer, the technical solution in the examples of thepresent invention will be clearly and completely described below. It isobvious that the described examples are one portion of the Examples ofthe present invention, but not all the examples. Based on the examplesof the present invention, all the other examples obtained withoutcreative labor by one of ordinary skill in the art fall into the scopeprotected by the present invention.

Sufficiently detailed description is made below to each specific exampleof the present application, such that one of ordinary skill in the arthaving related knowledge and techniques in the art can carry out thetechnical solution of the present application. It should be understoodthat other examples can also be used, or that modifications or changescan be made to the examples of the present application.

Judging from the current market and industry requirements, the synthesistechnology of existing commercially available products has higherdifficulty, with many steps, long processes, or special materialstructures that are not easy to obtain, resulting in high productioncosts for its products. In view of these problems, this application usesa new synthesis path to obtain products with different structures, whichreduces the synthesis difficulty, simples the step process and thusrelatively reduces the production cost, while maintaining thecomprehensive performance to meet the requirements. This is mainlydemonstrated in that: (1) the materials used are commercially availableconventional products and are easy to obtain; (2) the reactions thatperfluoropolyether is modified to give a new intermediate, and thereactions that the new intermediate is combined with silane couplingagents, are conventional chemical reactions, and the conditions of whichare mild and easy to control; (3) The synthesis of product requiresfewer steps, and the separation and purification steps are relativelysimple, so the production is more advantageous in cost.

For this, the present invention provides a perfluoropolyethergroup-containing silane compound represented by formula (1):

Rf—X¹—X²—NQ_(k)T_(2-k)  (1);

In the above formula, Rf isF—(CF₂)_(m)—(OC₄F₈)_(p)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F(CF₂)_(t)—,here, p, q, r and s p, q, r and s are separately independent and areintegers of 0 or more and 200 or less, the sum of p, q, r and s is atleast 1, the existing sequence and number of each repeating unit with p,q, r and s and bracketed with brackets are arbitrary in the formula; inand t are separately integers of 0 or more and 30 or less, Z is F orCF₃;

Rf may be the following formula (a) or (b):

CF₃—(OC₂F₄)_(r)—(OCF₂)_(s)—OCF₂—  (a):

wherein, the sum of r and s is an integer of 10 or more and 200 or less;

F—(CF₂)_(m)—(OC₄F₈)_(p)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F(CF₂)_(t);  (b):

Wherein, in and t are separately independent, in is an integer of 1-16,t is an integer of 0-2, r and s are separately independent and areintegers of 1 or more and 200 or less, the sum of p, q, r and s is 10 ormore and 200 or less, the existing sequence and number of each repeatingunit with p, q, r and s and bracketed with brackets are arbitrary in theformula.

In the forementioned formula (1), X¹ is a bivalent organic group;preferably X¹ is a group as shown below:—R⁴—X³—X⁴—; wherein, R⁴ is C₁₋₆alkyl or substituted C₁₋₆ alkyl; X³ is a group selected from —O—, —S—,ortho-, meta- or para-phenylene, ortho-, meta- or para-benzylidene,—C(O)O—, —CONR⁵—, —O—CONR⁵—, —NR⁵—, —Si(R⁶)₂—, —(Si(R⁶)₂O)_(f)— Si(R⁶)₂—and —(CH₂)_(g)—, R⁵, when present at each time, is separatelyindependent and is a hydrogen atom, phenyl or C₁₋₆ alkyl, R⁶ is C₁₋₆alkyl or substituted C₁₋₆ alkyl; X⁴ is a bivalent group; f, when presentat each time, is separately independent and is an integer of 1-100, g,when present at each time, is separately independent and is an integerof 1˜20;

In the forementioned formula (1), X² is carbonyl (—CO—), sulfuryl (—SO—)or anhydride.

In the forementioned formula (1), T, when present at each time, isseparately independent and is hydroxyl, hydrolysable group orhydrocarbon group; preferably, T, when present at each time, isseparately independent, and is selected from hydroxyl, —O (R⁷), C₁₋₁₂alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl and phenyl, R⁷ is C₁₋₁₂ alkyl. Morepreferably, T, when present at each time, is separately independent, andis hydroxyl, or —O(R⁷), R⁷ is C₁₋₁₂ alkyl.

In the forementioned formula (1), Q, when present at each time, isseparately independent and is —Y—SiR¹ _(j)R² _(3-j), wherein, Y, whenpresent at each time, is separately independent and is a bivalentorganic group; R¹, when present at each time, is separately independentand is alkoxy, hydroxyl or a group that can be hydrolyzed to hydroxylgroup; preferably, R¹ is —OR³, wherein, R³ is substituted orunsubstituted C₁₋₃ alkyl, preferably, R³ is methyl; wherein, R², whenpresent at each time, is separately independent and is C₁₋₂₂ alkyl, orQ′; wherein, Q′ and Q have the same meanings; j is separatelyindependent in each of Q and Q′, being an integer selected from 0˜3, thesum of j is 1 or more; k is separately independently 1 or 2, preferably,k is 2.

According to some preferred embodiments, the forementioned X⁴ is a groupas represented by —(R⁷)_(a)—(X⁵)_(b)—R⁸—; wherein, R⁷ is —(CH₂)_(c)—,ortho-, meta- or para-phenylene, or ortho-, meta- or para-benzylidene;R⁸ is —(CH₂)_(d)—, ortho-, meta- or para-phenylene, or ortho-, meta- orpara-benzylidene; X⁵ is —(X⁶)_(e)—; wherein, X⁶, when present at eachtime, is separately independent, and is a group selected from —O—, —S—,ortho-, meta- or para-phenylene, ortho-, meta- or para-benzylidene,—C(O)O—, —CONR⁵—, —O—CONR⁵—, —Si(R⁶)₂—, —(Si(R⁶)₂O)_(f)— Si(R⁶)₂— and—(CH₂)_(g)—; R⁵, when present at each time, is separately independent,and is a hydrogen atom, phenyl or C₁₋₆ alkyl; R⁶, when present at eachtime, is separately independent, and is phenyl or C₁₋₆ alkyl; f, whenpresent at each time, is separately independent, and is an integer of1˜100; g, when present at each time, is separately independent, and isan integer of 1˜20; c is an integer of 1˜20; d is an integer of 1˜20; eis an integer of 1˜10; a is 0 or 1; b is 0 or 1.

According to some preferred embodiments, the perfluoropolyethergroup-containing silane compound as represented by the forementionedformula (1) has the number average molecule weight of 500˜10,000,preferably 1000-8000, more preferably 3000-6000.

The present invention also provides a method for preparing aperfluoropolyether group-containing silane compound as represented bythe forementioned formula (1), the method comprises reacting Rf—X¹—X²—OHwith an acyl halogenation agent and an aminosilane coupling agent toproduce Rf—X¹—X²—NQ_(k)T_(2-k);

Rf—X¹—X²—OH acyl halogenation agent+aminosilane couplingagent→Rf—X¹—X²—NQ_(k)T_(2-k)

According to some preferred embodiments, the acyl halogenation agent isacyl halide, thionyl halide or phosphoryl halide, preferably acylchloride, sulfuryl chloride, phosphonyl chloride, more preferably acylchloride, most preferably oxaloyl chloride.

According to some preferred embodiments, the aminosilane coupling agentis HNQ_(k)T_(2-k), wherein Q is —Y—SiR¹ _(j)R² _(3-j), wherein, Y is abivalent organic group; R¹ is alkoxy, hydroxyl or a group that can behydrolyzed to hydroxyl group; preferably, R¹ is —OR³, wherein, R³ issubstituted or unsubstituted C₁₋₃ alkyl, preferably, R³ is methyl,ethyl, propyl or isopropyl; wherein, R² is C₁₋₂₂ alkyl, or Q′; wherein,Q′ and Q has the same meaning; j is separately independent in each of Qand Q′, being an integer selected from 0˜3, the sum of j is 1 or more; kis separately independently 1 or 2, preferably, k is 2; T is hydroxyl,hydrolysable group or hydrocarbon group; preferably, T is selected fromhydroxyl, —O(R⁷), C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl and phenyl,R⁷ is C₁₋₁₂ alkyl; more preferably, T is hydroxyl, or —O(R⁷), R⁷ isC₁₋₁₂ alkyl.

According to some preferred embodiments, the present invention providesa perfluoropolyether group-containing silane compound as represented byformula (2),

Wherein, Rf is

q, r and s are separately independent and are integers of 0 or more and200 or less, the sum of q, r and s is at least 1, the existing sequenceof each repeating unit noted with q, r or s and bracketed with bracketsis arbitrary in the formula; in is an integer of 1-16, t is 0 or 1, Z isa fluoride atom or trifluoromethyl;

X is a bivalent organic group;

T, when present at each time, is separately independent and is hydroxyl,hydrolysable group or hydrocarbon group;

Q, when present at each time, is separately independent and is —Y—SiR¹_(j)R² _(3-j);

Y, when present at each time, is separately independent and is abivalent organic group;

R¹, when present at each time, is separately independent and is alkoxy,hydroxyl or a group that can be hydrolyzed to hydroxyl group;

R², when present at each time, is separately independent and is C₁₋₂₂alkyl or Q′, Q′ and Q have the same meaning;

j is separately independent in each of Q and Q′, and is an integerselected from 0˜3, the sum of j is 1 or more;

k is separately independent, and is 1 or 2.

According to more preferred embodiment, in the forementioned formula(2), k is 2.

According to some preferred embodiments, in the forementioned formula(2), X is a group represented by —(R³)_(a)—(X¹)_(b)—R⁴—, wherein, R³ is—(CH₂)_(c)—, ortho-, meta- or para-phenylene, or ortho-, meta- orpara-benzylidene; R⁴ is —(CH₂)d-, ortho-, meta- or para-phenylene, orortho-, meta- or para-benzylidene; X¹ is —(X²)_(e)—, wherein X², whenpresent at each time, is separately independent, and is a group selectedfrom —O—, —S—, ortho-, meta- or para-phenylene, ortho-, meta- orpara-benzylidene, —C(O)O—, —CONR⁵—, —O—CONR⁵—, —NR⁵—, —Si(R⁶)₂—,—(Si(R⁶)₂O)_(f)—Si(R⁶)₂— and —(CH₂)_(g)—, wherein R⁵, when present ateach time, is separately independent, and is a hydrogen atom, phenyl orC₁₋₆ alkyl; R⁶, when present at each time, is separately independent,and is phenyl or C₁₋₆ alkyl; f, when present at each time, is separatelyindependent, and is an integer of 1˜100; g, when present at each time,is separately independent, and is an integer of 1˜20; c is an integer of1˜20; d is an integer of 1˜20; e is an integer of 1˜10; a is 0 or 1; bis 0 or 1.

According to some preferred embodiments, in the forementioned formula(2), X is C₁₋₂₀ alkylidene, —R³—X³—R⁴— or —X⁴—R⁴—, wherein, X³ is —O—,—S—, —C(O)O—, —CONR⁵—, —O—CONR⁵—, —Si(R⁶)₂—, —(Si(R⁶)₂O)_(f)—Si(R⁶)₂—,—O—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—,—CONR⁵—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—, —CONR⁵—(CH₂)_(h)—N(R⁵)— or—CONR⁵-(ortho-, meta- or para-phenylene)-Si(R⁶)₂—; X⁴ is —S—, —C(O)O—,—CONR⁵—, —O—CONR⁵—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—,—CONR⁵—(CH₂)_(h)—N(R⁵)— or —CONR⁵-(ortho-, meta- orpara-phenylene)-Si(R⁶)₂—; wherein R³ is —(CH₂)_(c)—, ortho-, meta- orpara-phenylene, or ortho-, meta- or para-benzylidene; R⁴ is—(CH₂)_(d)-ortho-, meta- or para-phenylene, or ortho-, meta- orpara-benzylidene; R⁵ is a hydrogen atom, phenyl or C₁₋₆ alkyl, R⁶ isphenyl or C₁₋₆ alkyl; c is an integer of 1˜20; d is an integer of 1˜20;f is an integer of 1˜100; h is an integer of 1˜20.

According to some preferred embodiments, in the forementioned formula(2), R³ is —(CH₂)_(c)—, R⁴ is —(CH₂)_(d)—, wherein, c is an integer of1˜20; d is an integer of 1˜20.

According to some preferred embodiments, in the forementioned formula(2), X is C₁₋₂₀ alkylidene, —(CH₂)_(c)—O—(CH₂)_(d),—(CH₂)_(c)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂— (CH₂)_(d)—, —(CH₂)_(c)—O—(CH₂)_(h)—(Si(R⁶)₂O)_(f)—Si(R⁶)₂—(CH₂)_(d)—, wherein, R⁶ is phenyl or C₁₋₆ alkyl;c is an integer of 1˜20; d is an integer of 1˜20; f is an integer of1˜100; h is an integer of 1˜20.

According to some preferred embodiments, in the forementioned formula(2), X is selected from the following groups: —CH₂—, —(CH₂)₂—, —(CH₂)₃—,—(CH₂)₄—, —(CH₂)₆—, —CH₂C₆H₄—, —CH₂OCH₂—, —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—, —CH₂C₆H₄—OCH₂—, —CONH—(CH₂)₃—, —CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃—, Ph is phenyl, —CON(CH₃)—(CH₂)₆—, —CON(Ph)-(CH₂)₆—, Phis phenyl, —CONH—(CH₂)₂NH(CH₂)₃—, —CONH—(CH₂)₆NH(CH₂)₃—,—CH₂O—CONH—(CH₂)₃—, —CH₂O—CONH—(CH₂)₆—, —C(O)O—(CH₂)₃—, —C(O)O—(CH₂)₆—,—S—(CH₂)₃—, —(CH₂)₂S(CH₂)₃—, —CH₂O—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—.

According to some preferred embodiments, in the forementioned formula(2), T, when present at each time, is separately independent and isselected from hydroxyl, —O (R⁷), C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂alkynyl and phenyl, R⁷ is C₁₋₁₂ alkyl; more preferably, T, when presentat each time, is separately independent and is hydroxyl, or —O (R⁷), R⁷is C₁₋₁₂ alkyl.

According to some preferred embodiments, in —Y—SiR¹ _(j)R² _(3-j) of Q,j is 3.

According to some preferred embodiments, the perfluoropolyethergroup-containing silane compound represented by the formula (2) has thenumber average molecule weight of 500˜10,000, preferably 1000-8000, morepreferably 3000-6000.

The present invention also provides a method for preparing aperfluoropolyether group-containing silane compound represented by theforementioned formula (2), the method comprises:

reacting and converting a compound of formula Rf—CH₂—O—X—COOH with anacyl halogenation agent and an aminosilane coupling agent to obtain aperfluoropolyether group-containing silane compound of formula (2),

Wherein, Rf is:

q, r and s are separately independent and are integers of 0 or more and200 or less, the sum of p, q, r and s is at least 1, the existingsequence of each repeating unit noted with q, r or s and bracketed withbrackets is arbitrary in the formula; in is an integer of 1-6, t is 0 or1, Z is a fluoride atom or trifluoromethyl;

X is a bivalent organic group;

T, when present at each time, is separately independent and is hydroxyl,hydrolysable group or hydrocarbon group;

Q, when present at each time, is separately independent and is —Y—SiR¹_(j)R² _(3-j);

Y, when present at each time, is separately independent and is abivalent organic group;

R¹, when present at each time, is separately independent and is alkoxy,hydroxyl or a group that can be hydrolyzed to hydroxyl group;

R², when present at each time, is separately independent and is C₁₋₂₂alkyl or Q′,

Q′ and Q have the same meaning;

j is separately independent in each of Q and Q′, and is an integerselected from 0˜3, the sum of j is 1 or more;

k is separately independent, and is 1 or 2.

According to some preferred embodiments, the acyl halogenation agent isacyl halide, preferably acyl chloride, and more preferably oxalylchloride.

According to some preferred embodiments, the aminosilane coupling agentis HNQ_(k)T_(2-k), wherein the meanings of Q, T, k are the same as thosedefined in the foremention formula (2).

According to some preferred embodiments, preparation process ofRf—CH₂—O—X—COOH comprises:

Step 1: first reacting the compound of formula Rf—CH₂OH with a base inthe presence of a solvent, and then making nucleophilic substitutionreaction with a compound of formula L-X-G, obtaining a compound offormula Rf—CH₂—O—X-G, wherein in the formula L-X-G, L is a leaving groupwhere a nucleophilic substitution reaction can occur, X is a bivalentorganic group, G is a group that can be hydrolyzed to carboxylic acid,

Step 2: chemically converting the compound of formula Rf—CH₂—O—X-G toobtain a compound of formula Rf—CH₂—O—X—COOH,

According to some preferred embodiments, the base in the forementionedstep 1 is selected from inorganic base or organic base; inorganic baseis preferably selected from at least one of LiOH, NaOH, KOH, K₂CO₃,Na₂CO₃, Cs₂CO₃, NaH, t-BuOK; organic base is preferably selected from atleast one of DIPEA, DBU, 1,1,3,3-tetramethylguanidine. More preferably,the base is selected from at least one of sodium hydroxide, potassiumhydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate,potassium carbonate and cesium carbonate.

According to some preferred embodiments, in the compound of formulaL-X-G of the forementioned step 1, L is selected from: chlorine atom,bromine atom, iodine atom, or other group(s) that can undergonucleophilic substitution reaction.

According to some preferred embodiments, in the compound of formulaL-X-G of the forementioned step 1, G is selected from: a group(s) ofester group, nitrile group, amide group, or substituted amide group.

According to some preferred embodiments, the base in step 2 is selectedfrom at least one of sodium hydroxide, potassium hydroxide, lithiumhydroxide and cesium hydroxide.

According to some preferred embodiments, the acid in step 2 is selectedfrom an inorganic acid such as hydrochloric acid, sulfuric acid,phosphoric acid or nitric acid.

According to some preferred embodiments, the present invention providesa perfluoropolyether group-containing silane compound represented byformula (3),

wherein, wherein, Rf isF—(CF₂)_(m)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—, q, r,and s are separately independent and are integers of 0 or more and 200or less, the sum of q, r and s is at least 1, the existing sequence ofeach repeating unit noted with q, r or s and bracketed with brackets isarbitrary in the formula; in is an integer of 1-16, t is 0 or 1, Z is afluoride atom or trifluoromethyl;

X is a bivalent organic group, preferably X is C₁₋₆ alkylidene,—CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent on phenyl ring;

Y¹, Y² are separately independently C₁₋₆ alkylidene;

Q¹, Q² are separately independently alkoxy, hydroxyl or a group that canbe hydrolyzed to hydroxyl group;

R¹, R² are separately independently C₁₋₆ alkyl or phenyl;

n is an integer of 1-3, preferably, n is 3.

According to more preferred embodiment, in the formula (3), Rf isCF₃(OC₂F₄)_(r)(OCF₂)_(s)OCF₂, wherein, r, s are separately independentand are integers of 0 or more and 200 or less, the sum of r, s is atleast 1, the existing sequence of each repeating unit noted with r, sand bracketed with brackets is arbitrary in the formula; preferably, thesum of r, s is at least 10, more preferably 10-100, and furtherpreferably 20-80, and most preferably 30-60;

X is C₁₋₆ alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent onphenyl ring;

Y¹, Y² are separately independently C₁₋₆ alkylidene;

Q¹, Q² are separately independently alkoxy, hydroxyl or a group that canbe hydrolyzed to hydroxyl group;

R¹, R² are separately independently C₁₋₆ alkyl or phenyl.

According to some preferred embodiments, the forementioned r, s areseparately independently integers of 0 or more and 100 or less, orintegers of 10-50, the sum of r, s is at least 10, or at least 20.

According to some preferred embodiments, in the forementioned formula(3), X is —CH₂— or —CH(CH₃)—.

According to some preferred embodiments, in the forementioned formula(3), Y¹ and Y² are separately —(CH₂)₃—.

According to some preferred embodiments, in the forementioned formula(3), Q¹, Q² are separately independently C₁₋₆ alkoxy.

According to some preferred embodiments, in the forementioned formula(3), Q¹, Q² are separately —OCH₃, —OC₂H₅, —OC₃H₇, —OC (CH₃)₂.

According to some preferred embodiments, in the forementioned formula(3), n is 3.

According to some preferred embodiments, the perfluoropolyethergroup-containing silane compound represented by the forementionedformula (3) has the number average molecule weight of 500˜10,000,preferably 1000-8000, more preferably 3000-6000.

According to some preferred embodiments, the present invention providesa method for preparing a perfluoropolyether group-containing silanecompound represented by the forementioned formula (3),

The method comprises: reacting Rf—CH₂—O—X—COOH with acyl halogenationagent and aminosilane coupling agent,

wherein, Rf isF—(CF₂)_(m)—(OC₃F₆)_(q)—(OC₂F₄)_(r)—(OCF₂)_(s)—OC(Z)F—(CF₂)_(t)—, q, r,and s are separately independent and are integers of 0 or more and 200or less, the sum of q, r and s is at least 1, the existing sequence ofeach repeating unit noted with q, r or s and bracketed with brackets isarbitrary in the formula; in is an integer of 1-16, t is 0 or 1, Z is afluoride atom or trifluoromethyl; or Rf isCF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂, wherein, r, s are separatelyindependently integers of 0 or more and 200 or less, the sum of r, s isat least 1, the existing sequence of each repeating unit noted with r, sand bracketed with brackets is arbitrary in the formula; preferably, thesum of r, s is at least 10, more preferably 10-100, further preferably20-80, most preferably 30-60;

X is a bivalent organic group, preferably X is C₁₋₆ alkylidene,—CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent on phenyl ring;

Y¹, Y² are separately independently C₁₋₆ alkylidene;

Q¹, Q² are separately independently alkoxy, hydroxyl or a group that canbe hydrolyzed to hydroxyl group;

R¹, R² are separately independently C₁₋₆ alkyl or phenyl;

n is an integer of 1-3, preferably, n is 3.

According to some preferred embodiments, the used acyl halogenationagent is not particularly limited, and for the above reaction, acylhalide, particularly acyl chloride, and more particularly oxalylchloride may be preferably used.

According to some embodiments, preparation process of Rf—CH₂—O—X—COOHcomprises:

Step 1: first reacting the compound of formula Rf—CH₂OH with a base inthe presence of a solvent, and then making a nucleophilic substitutionreaction with a compound of formula L-X-G, wherein, L is a leaving groupwhere a nucleophilic substitution reaction can occur, G is a group thatcan be hydrolyzed to carboxyl; X is a bivalent organic group, obtainingan esteryl perfluorinated polyether compound of formula Rf—CH₂—O—X-G,

Step 2: hydrolyzing the compound of formula Rf—CH₂—O—X-G to obtain acarboxyl perfluorinated polyether compound of formula Rf—CH₂—O—X—COOH,

Wherein, Rf, X, G have the same meanings as those defined in theforementioned formula (3).

According to some preferred embodiments, the base in step 1 is selectedfrom inorganic base or organic base; the inorganic base is preferablyselected from at least one of LiOH, NaOH, KOH, K₂CO₃, Na₂CO₃, Cs₂CO₃,NaH, t-BuOK; the organic base is preferably selected from at least oneof DIPEA, DBU, 1,1,3,3-tetramethylguanidine. More preferably, the baseis selected from: at least one of sodium hydroxide, potassium hydroxide,lithium hydroxide, cesium hydroxide, sodium carbonate, potassiumcarbonate and cesium carbonate.

According to some preferred embodiments, in the compound of theforementioned formula L-X-G, L is chlorine atom, bromine atom, or iodineatom.

According to some preferred embodiments, in the compound of theforementioned formula L-X-G, X is C₁₋₂₀ alkylidene, more preferably C₁₋₆alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which has a substitutent on phenylring.

According to some preferred embodiments, in the compound of theforementioned formula L-X-G, G is ester group, nitrile group, amidegroup, or substituted amide group. Further, the examples of the estermay be methyl ester, ethyl ester, propyl ester, isopropyl ester, benzylester, etc. The examples of the amides may be N-substituted amide orN,N-disubstituted amide.

According to some preferred embodiments, the examples of the compound ofL-X-G comprise but not limited to:

According to some preferred embodiments, the base in the forementionedstep 2 is selected from at least one of sodium hydroxide, potassiumhydroxide, lithium hydroxide and cesium hydroxide.

According to some preferred embodiments, the acid in the forementionedstep 2 is selected from an inorganic acid, and the examples of theinorganic acid may comprise hydrochloric acid, sulfuric acid, phosphoricacid or nitric acid.

According to some preferred embodiments, the acylating agent is acylhalide, preferably acyl chloride, and more preferably oxalyl chloride.

According to some preferred embodiments, the aminosilane coupling agentis preferably bis(alkoxy silane alkyl) amine, more preferably bis(alkoxysilane alkyl) amine.

According to one more preferred embodiment of the present invention, amethod for preparing a perfluoropolyether group-containing silanecompound comprises the following steps:

Step 1: first reacting a compound of formula Rf—CH₂OH with potassiumhydroxide at room temperature, and then making a nucleophilicsubstitution reaction with the compound of formula BrCH₂COOC₄H₉ atnormal or heated (preferably 25-75° C.) temperature, obtaining anesteryl perfluorinated polyether compound of formula Rf—CH₂OCH₂ COOC₄H₉,

Rf is CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂—, r+s is 35-85, which has a numberaverage molecule weight of 3000-8000;

Step 2: reacting the esteryl perfluorinated polyether compound offormula Rf—CH₂—OCH₂ COOC₄H₉ with a base to be hydrolyzed, addinghydrochloric acid to adjust acidity, separating and obtaining a carboxylperfluorinated polyether compound of formula Rf—CH₂—O—CH₂COOH,

Step 3: reacting a carboxyl perfluorinated polyether compound of formulaRf—CH₂—O—CH₂COOH with oxalyl chloride at a temperature of 25-50° C.,then reacting and converting it with bis(trimethylsilane propyl) amineat room temperature to obtain a perfluoropolyether silane compound offormula Rf—CH₂—O—CH₂CON[CH₂CH₂CH₂Si(OCH₃)₃]₂.

In the preparation process of the present invention, there is nolimitation to the solvent used, as long as it is a solvent that candissolve perfluorinated polyether alcohol, esteryl polyfluorinatedpolyether compound, carboxyl polyfluorinated polyether compound and thelike under the condition of normal temperature or heating. It ispreferably a fluorinated solvent, such as hydrofluoroether, fluorinatedhydrocarbon, etc., and more preferably nonafluorobutyl ethyl ether,nonafluorobutyl methyl ether, perfluorohexane, m-trifluorotoluene, etc.

The preparation process of the present invention may be conducted underthe condition of normal temperature or heating. It is preferred that thenucleophilic substitution reaction of perfluorinated polyether alcoholin step 1 may be conducted at 25-75° C., and it is preferred that theacyl halogenation reaction in step 3 may be conducted at 25-50° C.

As described above, in the present invention, an esteryl perfluorinatedpolyether compound of formula Rf—CH₂—O—X-G is obtained by making anucleophilic substitution reaction with a compound of formula Rf—CH₂OHand a compound of formula L-X-G, wherein, L is a leaving group where anucleophilic substitution reaction can occur, G is a group that can behydrolyzed to carboxyl, X is a bivalent organic group, and then acompletely new intermediate carboxyl perfluorinated polyether compoundof formula Rf—CH₂—O—X—COOH is obtained by hydrolyzation. Since theperfluorinated polyether group is connected to the carboxyl groupthrough the spacing group X, the subsequent further reactions of thecarboxyl group become easy to be realized, such as reaction with theaminosilane coupling agent can obtain the perfluorinated polyethergroup-containing amino silane compound of the invention. Theintermediate of formula Rf—CH₂—O—X—COOH can be used as a startingmaterial to easily perform further follow-up reactions of carboxylgroups, thereby obtaining a variety of derivative compounds containingperfluorinated polyetheryl and carbonyl group(s). For example, thecarboxyl group can react with the acyl halogenation agent to formacylhalide, condense with the carboxylate to form anhydride, condensewith alcohols to form esters, react with amines to form amides, andprimary amides can also be dehydrated so as to be prepared into nitrile.

Since the perfluoropolyether group-containing silane compound obtainedby the present invention is a specific perfluoropolyethergroup-containing amino siloxane compound, it is suitable for use as asurface treatment agent. The surface treatment agent may comprise amixture of one or more of the perfluoropolyether group-containing silanecompounds of the present invention and a liquid medium such as anorganic solvent. The organic solvent may be a variety of solvents whichcapable of dissolving the compound under the condition that the solventdoes not react with the compound of the invention. Examples of theorganic solvents include fluorinated solvents, such as fluorinatedalkanes, fluorinated halogenated hydrocarbons, fluorinated aromatichydrocarbons, such as hydrofluoroether, etc., and may also be acombination of different solvents. The concentration of theperfluoropolyether group-containing silane compound of the presentinvention in the surface treatment agent can be adjusted as needed,usually 0.01-30 wt %, preferably 0.05-20 wt %, and more preferably 10-20wt %. According to the different coating methods used, differentconcentrations are selected, for example, high concentrations aresuitable for dry coating and low concentrations are suitable for wetcoating. It can also be prepared into high concentrations and dilutedwhen used according to the needs of the coating method.

When the surface treatment agent of the invention is used to treat thesurface, even if the resulting layer is only a few nanometers thick, asurface having a water contact angle of 110 degrees or more, preferably115 degrees or more, and a dynamic friction coefficient of less than0.05 can be formed, as shown in the following examples.

There is no particular limit to the substrate which is treated by thesurface treatment agent of the present invention to form a surfacetreatment layer. Examples thereof can include optical components, cellphones, tablet computers, etc., including inorganic substrates such asglass plates, glass plates containing inorganic layers, and ceramics;and organic substrates such as transparent plastic substrates andtransparent plastic substrates containing inorganic layers.

There is no particular limit to the method for forming a treatmentlayer. For example, wet coating method and dry coating method can beused. Examples of wet coating method include dip coating, spin coating,flow coating, spray coating, roll coating, photo concave coating, andthe like. Examples of dry coating method include vacuum evaporation,sputtering, CVD, and the like. Specific examples of vacuum evaporationmethod include resistance heating, electron beam, high-frequencyheating, ion beam, and the like. Examples of CVD method include plasmaCVD, optical CVD, thermal CVD, and the like.

After forming a treatment layer on the substrate by a dry or wet coatingmethod, heating, humidifying, light radiation, electron beam radiation,and the like can be carried out if necessary.

There is no particular limit to the thickness of the treatment layerformed by using a surface treatment agent containing the perfluorinatedpolyetheryl silane compound of the present invention. According to thedust proof, rubbing resistance and optical performance of opticalcomponents and screens of mobile phones and tablet computers, it ispreferably 1-30 nm, more preferably 3-20 nm, and further preferably 5-10nm.

When the surface treatment agent containing the above-mentionedperfluorinated polyetheryl silane compound of the present invention isused on the substrate such as various optical components(anti-reflective films, optical filters, optical lenses, eyeglasslenses, spectroscopic lenses, spectroscopes, prisms, mirrors, etc.) andthe screens of mobile phones, a tablet computer, etc. to form atreatment layer, adhesion of dirt or moisture such as fingerprints, skinoil, sweat, cosmetics etc. may be prevented without degrading theoptical properties of the optical elements and the screens. Even if dirtand moisture are adhered, they can be easily erased, and the treatmentlayer is scrape resistant, etc., thus resulting in that the treatmentlayer have excellent durability and can meet the requirements ofanti-fouling, anti-fingerprint, scrape resistance, high smoothness andwear durability of optical components and cell phones, tablet computers,etc.

EXAMPLES Synthesis Example 1

A perfluoropolyether group-containing silane compound A1 is synthesizedaccording to the following steps

Step 1:

10 g perfluoropolyether modified alcohol (a number average moleculeweight of 3500˜4000) with an average composition ofCF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OH (the sum of r, s is 35-42), 15 mL1,3-bis(trifluoromethyl) benzene, 5 mL ethylene glycol dimethyl ether,2.6 g 50 wt % potassium hydroxide solution are added into a 100-mLthree-neck round-bottom flask equipped with a stirrer, and stirred atroom temperature for 3 hours. 3.8 mL tert-butyl bromoacetate, and 0.42 gtetrabutylammonium bromide is then sequentially added into the reactionflask, and stirred at 50° C. for 5 hours. After extraction with waterand decompression distillation, a colorless transparent product 9.6 g isobtained, i.e., an esteryl perfluoropolyether compound (M1):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂COOC₄H₉.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement of the newly-added structures is shown in        the table below.

Group structure δ, ppm CH₂— 4.136 (s) —CF₂CH₂— 4.058~3.996 (q) —COOC₄H₉1.498 (s)

Step 2:

9.6 g esteryl perfluoropolyether compound (M1) obtained in step 1, 17 g10 wt % potassium hydroxide solution are added into a 100-mL three-neckround-bottom flask equipped with a thermometer and a stirrer, andstirred at 100° C. for 3 hours. After being reduced to room temperature,10 mL tetrahydrofuran is added, and after being adjusted to be acidicwith 2N hydrochloric acid, 30 mL hydrofluoroether HFE-7200 (produced by3M Company) is added and stirred. The non-fluorine phase (i.e., theupper solution) is removed, and the fluorine phase is washed 2 timeswith 2N hydrochloric acid, and finally the colorless transparent product9.0 g is obtained by decompression distillation, i.e., a carboxylperfluorinated polyether compound (M2):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂COOH.

By identification with a NMR spectrometer, the characteristic ¹Hchemical displacement of the newly-added structures is shown in thetable below.

Group structure δ, ppm —OCH₂— 4.308 (s) —CF₂CH₂— 4.063~4.001 (q)

Step 3

9.0 g carboxyl perfluorinated polyether compound (M2) obtained in step 2dissolved in 15 mL 1,3-bis(trifluoromethyl) benzene, 0.3 mL oxalolchloride, are added into a 100 mL four-neck round-bottom flask equippedwith a drop funnel, a thermometer and a stirrer, 0.2 mL DMF dissolved in5 mL 1,3-bis(trifluoromethyl) benzene is slowly added dropwise via thedrop funnel, then warmed up to 50° C. and stirred for 4 hours. Afterreduced to room temperature, it is slowly added dropwise into a 250-mLthree-neck round-bottom flask filled with 5 1,3-bis(trifluoromethyl)benzene, 4.2 mL diisopropyl ethylamine, 4 mL bis(3-trimethyloxy silylpropyl) amine, and stirred at room temperature for 5 hours. 40 mLperfluorohexane is added and extracted three times with 18 mL methanol.The fluorine phase is distilled under decompression to remove thevolatile components to give a colorless to pale yellow product, i.e.,the following perfluoropolyether group silane compound withtrimethoxylsilane at the end (A1):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂CON[(CH₂CH₂CH₂Si(OCH₃)₃]₂.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement of the newly-added structures is shown in        the table below.

Group structure δ, ppm —OCH₂— 4.469 (s) —CF₂CH₂— 4.197~4.118 (q)—Si(OCH₃)₃ 3.658~3.636 (d) —CH₂CH₂CH₂ Si(OCH₃)₃ 3.477~3.262 (m)—CH₂CH2CH₂Si(OCH₃)₃ 1.868~1.769 (m) —CH₂CH₂CH₂Si(OCH₃)₃ 0.745~0.669 (m)

Synthesis Example 2

A perfluoropolyether group-containing silane compound A2 is synthesizedaccording to the following steps

Step 1:

10 g perfluoropolyether modified alcohol (a number average moleculeweight of 4500˜5000) with an average composition ofCF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OH (a range of r+s is 35-42), 15 mL1,3-bis(trifluoromethyl) benzene, 5 mL ethylene glycol dimethyl ether,2.6 g 50 wt % potassium hydroxide solution are added into a 100-mLthree-neck round-bottom flask equipped with a stirrer, and stirred atroom temperature for 3 hours. 3.2 mL tert-butyl bromoacetate, and 0.32 gtetrabutylammonium bromide is then sequentially added into the reactionflask, and stirred at 50° C. for 5 hours. After extraction with waterand decompression distillation, a colorless transparent product 9.6 g isobtained, i.e., an esteryl perfluoropolyether compound (M3):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂COOC₄H₉

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement thereof is shown in the table below.

Group structure δ, ppm —OCH₂— 4.140 (s) —CF₂CH₂— 4.065~4.003 (q)—COOC₄H₉ 1.501 (s)

Step 2:

9.6 g esteryl perfluoropolyether compound (M3) obtained by step 1, 17 g10 wt % potassium hydroxide solution are added into a 100-mL three-neckround-bottom flask equipped with a thermometer and a stirrer, andstirred at 100° C. for 10 hours. After being reduced to roomtemperature, 10 mL tetrahydrofuran is added, and after being adjusted tobe acidic with 15% hydrochloric acid, 30 mL hydrofluoroether HFE-7200(produced by 3M Company) is added and stirred. The non-fluorine phase(i.e., the upper solution) is removed, the fluorine phase is washed 2times with 2N hydrochloric acid, and finally the colorless transparentproduct 9.0 g is obtained by decompression distillation, i.e., acarboxyl perfluorinated polyether compound (M4):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂COOH.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement is shown in the table below.

Group structure δ, ppm —OCH₂— 4.310 (s) —CF₂CH₂— 4.069~3.998 (q)

Step 3

9.0 g carboxyl perfluorinated polyether compound (M4) obtained in step 2dissolved in 18 mL 1,3-bis(trifluoromethyl) benzene, 0.23 mL oxalolchloride, are added into a 100 mL four-neck round-bottom flask equippedwith a drop funnel, a thermometer and a stirrer, 0.15 mL DMF dissolvedin 5 mL 1,3-bis(trifluoromethyl) benzene is slowly added dropwise viathe drop funnel, and then warmed up to 50° C. and stirred for 4 hours.After being reduced to room temperature, it is slowly added dropwiseinto a 250-mL three-neck round-bottom flask filled with 9 mL1,3-bis(trifluoromethyl) benzene, 1.6 mL diisopropyl ethylamine, 2.9 mLbis(3-trimethyloxy silyl propyl) amine, and stirred at room temperaturefor 5 hours. 72 mL perfluorohexane is added and extracted three timeswith 43 mL methanol. The fluorine phase is distilled under decompressionto remove the volatile components to give a colorless to pale yellowproduct, i.e., the following perfluoropolyether group silane compoundwith trimethoxylsilane at the end (A2):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂CON[(CH₂)₃Si(OCH₃)₃]₂.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement thereof is shown in the table below.

Group structure δ, ppm —OCH₂— 4.468 (s) —CF₂CH₂— 4.177~4.117 (m)—Si(OCH₃)₃ 3.656~3.634 (d) —CH₂CH₂CH₂ Si(OCH₃)₃ 3.468~3.270 (m)—CH₂CH₂CH₂Si(OCH₃)₃ 1.851~1.771 (m) —CH₂CH₂CH₂Si(OCH₃)₃ 0.730~0.667 (m)

Synthesis Example 3

A perfluoropolyether group-containing silane compound A3 is synthesizedaccording to the following steps

Step 1:

3 g perfluoropolyether modified alcohol (the number average moleculeweight of 3500˜4000) with an average composition ofCF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OH (a range of r+s is 35-42), 9 mL 7200and 3 mL t-BuOH solvent are added into a 100-mL three-neck round-bottomflask equipped with a stirrer, followed by addition of 0.45 g t-BuOK,and stirred at room temperature for 1.5 hours. 1.5 g BrCH₂C₆H₄COOC₄H₉,0.12 g tetrabutylammonium bromide is then sequentially added into thereaction flask, and stirred at 50° C. for 1.5 hours. After extractionwith water and decompression distillation, a colorless transparentliquid (M5) is obtained:CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂C₆H₄COOC₄H₉.

The resulting colorless transparent liquid (M5) is added into a 100-mLthree-neck round-bottom flask equipped with a thermometer and a stirrer,9 mL 20 wt % potassium hydroxide solution is added and stirred at 115°C. for 5 hours. After being reduced to room temperature and adjusted tobe acidic with 2N hydrochloric acid, the distilled water andtetrahydrofuran are added for extraction. The colorless transparentproduct 2.63 g is obtained by decompression distillation, i.e., acarboxyl perfluorinated polyether compound (M6):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂C₆H₄COOH.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement thereof is shown in the table below.

Group structure δ, ppm —C₆H₄— 8.105 (d)/7.576 (d) —OCH₂— 4.949 (s)—CF₂CH₂— 4.099~4.040 (m)

Step 2:

2.0 g carboxyl perfluorinated polyether compound (M6) dissolved in 6 mL1,3-bis(trifluoromethyl) benzene, 70 μL oxalol chloride and 40 μl DMF,are added into a 100 mL four-neck round-bottom flask equipped with adrop funnel, a thermometer and a stirrer, and then warmed up to 50° C.and stirred for 5 hours. After being reduced to room temperature, it isslowly added dropwise into a 25 mL three-neck round-bottom flask filledwith 2 mL 1,3-bis(trifluoromethyl) benzene, 0.72 mL triethylamine, 0.85mL bis(3-trimethyloxy silyl propyl) amine, and stirred at roomtemperature for 5 hours. 10 mL perfluorohexane is added and extractedfive times with 4 mL methanol. After being filtered with filtrationmembrane, it is distilled under reduced pressure to remove the volatilecomponents to give a colorless transparent product 1.2 g, i.e., thefollowing perfluoropolyether group silane compound withtrimethoxylsilane at the end (A3):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂C₆H₄CON[(CH₂)₃Si(OCH₃)₃]₂.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement thereof is shown in the table below.

Group structure δ, ppm —C₆H₄— 7.512 (m) —OCH₂— 4.872 (s) —CF₂CH₂— 4.014(m) —Si(OCH₃)₃/—CH₂CH₂CH₂— 3.683~3.416 (m) —CH₂CH₂CH₂Si(OCH₃)₃1.985~1.787 (m) —CH₂CH₂CH₂Si(OCH₃)₃ 0.891~0.509 (m)

Synthesis Example 4

A perfluoropolyether group-containing silane compound M2 is synthesizedaccording to the following steps

1 g perfluoropolyether modified alcohol (the number average moleculeweight of 3500˜4000) with an average composition ofCF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OH (a range of r+s is 35-42), 1.5 mL1,3-bis(trifluoromethyl) benzene, and 0.5 mL ethylene glycol dimethylether are added into a 100-mL three-neck round-bottom flask equippedwith a stirrer, and stirred at room temperature, followed by addition of0.09 g sodium hydride with bubble formation observed. 0.199 g ClCH₂CN,and 0.044 g tetrabutylammonium bromide are then sequentially added intothe reaction flask, and stirred at 50° C. for 3 hours. 5 mLhydrofluoroether HFE-7200 is added, and a light yellow transparentsolution is obtained via filtration of filtration membrane. Afterextraction with water and decompression distillation, a yellow-brownproduct (M7): CF₃(OCF₂CF₂)_(r)(OCF₂)_(s) OCF₂CH₂OCH₂CN, followed byaddition of 3 g 20% potassium hydroxide solution and reflux hydrolysisat 115° C. 0.74 g product is given by acidification and purification,i.e., a carboxyl perfluoropolyether compound (M2):CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂COOH.

-   -   By identification with a NMR spectrometer, the characteristic ¹H        chemical displacement thereof is shown in the table below.

Group structure δ, ppm —CF₂CH₂— 4.063~4.001 (q) —OCH₂— 4.308 (s)

-   -   By identification with a Fourier transform infrared        spectrometer, the structural characteristics absorption peaks        thereof is shown in the table below

Group structure ν, cm⁻¹ —COOH 2900~3100 (O—H stretch) —COOH 1739 (C═Ostretch) C—O/C—F 1040~1335 (perfluoropolyether characteristic band)

The resulting M2 may be further reacted as described in step 3 inSynthesis Example 1 to obtain A1:CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂CON[(CH₂CH₂CH₂Si(OCH₃)₃]₂.

Examples 1-3

The synthesized compounds A1, A2 and A3 and hydrofluoroether (3MCompany, Novec HFE7200) are formulated into 20% mass concentration assurface treatment agent (1), surface treatment agent (2) and surfacetreatment agent (3); the above surface treatment agents are vaporizedonto a chemically reinforced glass by vacuum deposition. At a vacuumpressure of less than 4×10⁻³ Pa, silicon dioxide is first deposited at athickness of 10 nm to the chemically reinforced glass by electron beamdeposition method to form a silicon dioxide membrane. The above surfacetreatment agens are deposited on each chemically reinforced glass at athickness of about 8 to 10 nm is by vacuum deposition. Then, thechemically reinforced glass with the deposition film attached issolidified in an environment of 60% humidity and 70° C. for 2 hours toform a surface treatment layer.

Comparison Examples 1 to 3

The surface treatment layers are formed according to the same method asdescribed in Example 1, excepting for replacing the surface treatmentagents (1-3) formulated with the compounds A1, A2 and A3 with thefollowing commercially available surface treatment agents 1 to 3.

Control surface treatment agent 1: Optool UD 509 (produced by DaikinIndustries, Ltd.)

Control surface treatment agent 2: Optool DSX-E (produced by DaikinIndustries, Ltd.)

Control surface treatment agent 3: X-71-195 (Shin-Etsu Chemical Co.,Ltd.)

Comparison Example 4

The surface treatment agent is formulated and the surface treatmentlayer is formed according to the same method as described in Example 1,excepting for replacing compound (A1) with the following controlcompound 1.

CF₃(OCF₂CF₂)_(r)(OCF₂)_(s)OCF₂CH₂OCH₂CH₂CH₂Si(OCH₃)₃.  Control Compound1:

Examples 4-6

The surface treatment agents (1-3) are dissolved in hydrofluoroether (3MCompany, Novec HFE7200) at a 0.4% mass concentration to be prepared intothe surface treatment agents (4-6); using a commercially available spraycoating device, the surface treatment agents (4-6) are uniformly spraycoated on chemically reinforced glass with a flow rate of 50 mg/sec anda conveying line speed of 13 mm/sec. Before coating, the chemicallyreinforced glass surface needs to be plasma treated. Then, thechemically reinforced glass with the spray treatment film attached issolidified in an environment of 60% humidity and 70° C. for 2 hours toform a surface treatment layer.

The surface treatment layer formed on the surface of the substrate isevaluated by the following methods. The results are shown in Tables 1 to3.

1. Evaluation of Hydrophobicity and Oleophobicity

The contact angle of the surface treatment layer to water and thecontact angle to n-hexadecane are measured using the contact anglemeasuring device (Beijing Harko Company, HARKE-DWA).

2. Determination of Smoothness

Using the friction coefficient instrument (Jinan Sanquan ZhongshiCompany, MXS-05A), the dynamic friction coefficient of the relativepublic paper (Daboai) is tested under the following conditions.

Contact area: 63 mm×63 mm;

Load: 200 g

Line speed: 100 mm/min

Stroke: 30 mm

3. Evaluation of Abrasion Resistance

The water contact angle of the surface treatment layer after abrasion isevaluated using the abrasion tester (Taber Company, 5900) under thefollowing conditions. After 1000 rounds for each time, the water contactangle is determined (when the water contact angle is less than 100degrees or after being subjected to 20,000 frictions or steel wooldamage, evaluation is terminated).

(1). Steel Wool Abrasion Resistance

Steel wool: BONSTAR #0000

Load: 1 kg/cm²

Moving stroke: 40 mm

Moving speed: 60 rpm

(2). Eraser Abrasion Resistance

Eraser: Minoan MB006004, 6.0 mm

Load: 1 kg

Moving stroke: 40 mm

Moving speed: 40 rpm

TABLE 1 Hydrophobicity, oleophobicity and smoothness DynamicHydrophobicity Oleophobicity friction (°) (°) coefficient Example 1 11770 0.03 Example 2 116 76 0.04 Example 3 116 76 0.04 Example 4 116 680.04 Example 5 116 69 0.05 Example 6 113 70 0.05 Comparison 115 69 0.04Example 1 Comparison 114 68 0.07 Example 2 Comparison 117 68 0.03Example 3 Comparison 115 68 0.03 Example 4

TABLE 2 Steel wool abrasion resistance Steel wool abrasion resistance(°) Comparison Comparison Comparison Comparison Friction Example ExampleExample Example Example Example Example Example Example Example times 12 3 4 5 6 1 2 3 4 0 117 116 116 116 116 113 116 114 117 115 1000 116 114114 116 114 112 115 111 116 112 2000 116 115 115 115 112 110 114 108 115111 3000 116 114 114 115 110 113 114 108 115 108 4000 116 114 115 114112 109 114 108 114 103 5000 115 113 112 114 110 112 113 106 114 97 6000115 114 114 114 110 107 113 102 114 — 7000 115 113 109 113 111 111 11399 114 — 8000 115 111 113 113 109 105 112 — 113 — 9000 115 111 111 113110 100 112 — 113 — 10000 113 112 110 113 109 110 112 — 113 — 13000 113111 111 112 109 111 112 — 113 — 16000 110 112 111 112 110 109 111 — 112— 18000 109 110 <100 110 109 98 110 — 111 — 20000 108 109 — 110 109 105110 — 110 —

TABLE 3 Eraser abrasion resistance Water contact angle (°) ComparisonComparison Comparison Comparison Friction Example Example ExampleExample Example Example Example Example Example Example times 1 2 3 4 56 1 2 3 4 0 117 115 115 117 116 114 116 114.02 117 114 1000 116 113 113114 113 112 113 109.1 113 103 2000 116 112 112 111 111 110 111 101.98105 102 3000 115 113 113 110 107 108 108 97.18 93 94 4000 112 111 111108 104 108 104 — — — 5000 112 112 112 108 84 107 84 — — — 6000 112 112112 107 — 103 — — — — 7000 109 108 108 106 — 97 — — — — 8000 108 102 102102 — — — — — —

As can be seen from the above Examples, the surface treatment agentprepared by the perfluorinated polyether compound of the presentinvention makes the glass substrate treated be excellent inanti-fouling, anti-fingerprint, scrape resistant and abrasion resistantperformances, and the comprehensive performance thereof is superior tothat of the commercially available product. Moreover, the preparation ofthe compound of the present invention is simple in process, easy tooperate and implement.

The above Examples are only for the purposes of illustrating the presentinvention, and are not limitations to the present invention. Ordinarytechnical persons in the relevant technical field may also make variouschanges and variation without departing from the scope of the presentinvention. Therefore, all equivalent technical solutions shall alsobelong to the scope disclosed in the invention.

1. A perfluoropolyether group-containing silane compound represented byformula (3),

wherein, Rf is CF₃(OC₂F₄)_(r)(OCF₂)_(s)OCF₂, wherein, r, s areindependently integers of 0 or more and 200 or less, the sum of r and sis at least 1, the sequence of each repeating unit noted with r, s andbracketed with brackets is arbitrary in the formula; in the formula, Xis C₁₋₆ alkylidene, —CH₂C₆H₄— or —CH₂C₆H₄— which has a substituent onphenyl ring; Y¹, Y² are independently C₁₋₆ alkylidene; Q¹, Q² areindependently hydroxyl or a group that can be hydrolyzed to hydroxylgroup; R¹, R² are independently C₁₋₆ alkyl or phenyl; n is an integer of1-3.
 2. The perfluoropolyether group-containing silane compoundaccording to claim 1, wherein when Rf is CF₃(OC₂F₄)_(r)(OCF₂)_(s)OCF₂,the sum of r and s is 20-100.
 3. The perfluoropolyether group-containingsilane compound according to claim 1, wherein n is
 3. 4. Theperfluoropolyether group-containing silane compound according to claim1, wherein X is —CH₂—, —CH(CH₃)— or —CH₂C₆H₄—.
 5. The perfluoropolyethergroup-containing silane compound according to claim 1, wherein Y¹ and Y²are independently —(CH₂)₃—.
 6. The perfluoropolyether group-containingsilane compound according to claim 1, wherein Q¹, Q² are independentlyC₁₋₆ alkoxy.
 7. The perfluoropolyether group-containing silane compoundaccording to claim 1, wherein Q¹, Q² are independently —OCH₃,—OCH(CH₃)₂, —OC₂H₅ or —OC₃H₇.
 8. The perfluoropolyether group-containingsilane compound according to claim 1, wherein the silane compound hasthe number average molecule weight of 500˜10,000.
 9. A method forpreparing a perfluoropolyether group-containing silane compoundrepresented by the formula (3) of claim 1,

the method comprising: reacting Rf—CH₂—O—X—COOH with an acylhalogenation agent and an aminosilane coupling agent,

wherein, the definition of each symbol is the same as the definition ofclaim
 1. 10. The method according to claim 9, wherein the acylhalogenation agent is (COCl)₂, SOCl₂, POCl₃, PCl₅ or SOBr₂.
 11. Themethod according to claim 9, further comprising: Step 1: first reactingthe compound of formula Rf—CH₂OH with a base in the presence of asolvent, and then making nucleophilic substitution reaction with acompound of formula L-X-G, wherein, L is a leaving group or atom where anucleophilic substitution reaction can occur, G is a group that can behydrolyzed to carboxylic acid; the definition of X is the same as any ofclaims 1-8; obtaining an esteryl perfluorinated polyether compound offormula Rf—CH₂—O—X-G,

Step 2: hydrolyzing the compound of formula Rf—CH₂—O—X-G to obtain acarboxyl perfluorinated polyether compound of formula Rf—CH₂—O—X—COOH


12. The method according to claim 11, wherein the base in step 1 isselected from inorganic base or organic base; the inorganic base isselected from at least one of LiOH, NaOH, KOH, K₂CO₃, Na₂CO₃, Cs₂CO₃,NaH, t-BuOK; the organic base is preferably selected from at least oneof DIPEA, DBU, or 1,1,3,3-tetramethylguanidine.
 13. The method accordingto claim 11, wherein, in the compound of the formula L-X-G, L ischlorine atom, bromine atom, or iodine atom.
 14. The method according toclaim 11, wherein, in the compound of the formula L-X-G, G is estergroup, nitrile group, or amide group.
 15. The method according to claim11, wherein the solvent is hydrofluoroether or fluorinated hydrocarbon.16. The method according to claim 11, wherein the base in step 2 isselected from at least one of sodium hydroxide, potassium hydroxide,lithium hydroxide, cesium hydroxide.
 17. The method according to claim11, wherein the acid in step 2 is selected from inorganic acid.
 18. Themethod according to claim 11, wherein the acid in step 2 is selectedfrom at least one of hydrochloric acid, sulfuric acid or nitric acid.19. The method according to claim 9, wherein the aminosilane couplingagent is bis(alkoxy silane alkyl)amine.
 20. A surface treatment agent,comprising the perfluoropolyether group-containing silane compound ofclaim
 1. 21. The surface treatment agent according to claim 20, whereinthe surface treatment agent comprises a fluorinated solvent.
 22. Thesurface treatment agent according to claim 20, wherein the fluorinatedsolvent is hydrofluoroether.
 23. The surface treatment agent accordingto claim 20, wherein the surface treatment agent contains 0.01-30 wt %perfluoropolyether group-containing silane compound.
 24. The surfacetreatment agent according to claim 20, wherein the surface treatmentagent contains 0.05-20 wt % perfluoropolyether group-containing silanecompound.
 25. The surface treatment agent according to claim 20, whereinthe surface treatment agent contains 10-20 wt % perfluoropolyethergroup-containing silane compound.
 26. An article, wherein having acoating formed by the surface treatment agent of claim 21, and a watercontact angle thereof is at least 110 degrees, and a dynamic frictioncoefficient is no more than 0.05.
 27. The article according to claim 26,wherein the article is an optical component, a display screen of a smartphone, a tablet or computer.